Dry free-flowing detergent composition and method of preparation



United States Patent 3,223,646 DRY FREE-FLOWING DETERGENT COMPOSITION AND METHOD OF PREPARATION James Cline McKenna, Shaker Heights, Kurt Albrecht, Painesville, and John H. McCracken, Madison, Ohio, assignors to Diamond rattlkali Company, Cleveland, Ohio a cor oration of De aware No D rawin g. Filed Aug. 25, 1961, Ser. No. 133,773 7 Claims. (Cl. 252-135) This invention relates to detergent compositions and more particularly to detergent composition-s having specific applicability as so-called hard-surface cleaners, and to the method of preparing such compositions.

Detergent compositions which are applicable for use as hard-surface cleaners differ from other types of detergents, particularly those used for textile cleaners. The principal difference of the socalled hard-surface cleaners is that they generally contain little or no organic substituents, i.e., materals such as the alkyl aryl sulfonates, which make up a major portion of other detergents, particularly those used for textile cleaning. In contrast, the hard-surface type detergent compositions contain alkaline carbonates, phosphates and sometimes silicates, as the principal ingredients thereof. Perhaps the most widely used of such inorganic ingredients are the alkali metal carbonates, such as soda ash, the sesquicarbonates, typically sodium sesquicarbonate, and the alkali metal orthophosphates, typically trisodium orthophosphate. These materials provide water softening characteristics in the composition as well as some detergency. Additionally, these hard-surface cleaning detergent compositions contain various condensed and crystalline phosphates, such as the alkali metal tripolyphosphates, typically sodium tripolyphosphate, and trisodium phosphate, which have good water softening properties. The various pyrophosphates, such as sodium pyrophosphate, are also used, which materials generally have a higher detergency than the tripolyphosphates, although their water softening ability is somewhat less. If desired, these compositions may also contain various silicate materials such as metaand ortho-silicates, and liquid silicates, as well as anionic, cationic, and nonionic surfactant materials, which latter materals are generally present in amounts not in excess of about by weight of the total composition.

Heretofore, it has been the practice to form a mechanical mix of the desired phosphates, such as trisodium phosphate and/or sodium tripolyphosphate, and the alkaline carbonate material, such as sodium carbonate. In this dry mix is also included any other materials which may be desired, such as silicates and/or various anionic, cationic, and non-ionic surfactant material-s. Although, from the standpoint of cleaning efi'iciency, such a composition has been found to be satisfactory, the thus-formed dry, mechanical mix is subject to some disadvantages.

The principal disadvantage encountered is, of course, that by means of mechanical mixing it is not possible to obtain a completely homogeneous material. Accordingly, no matter how long the various constituents of the detergent composition are mixed and blended, the composition of the final product is not completely homogeneous. These products, upon vibration and shaking over a period of time, as for example, in transit to either wholesale or retail outlets, undergo a phenomenon known as layering. In such instances, these is a settling of the heavier particles of material in the composition to the bottom portion of the container while the lighter materials remain in a separate layer in the top portion of the container. Thus, when one goes to use a quantity of this material, which is less than the entire contents of the container, the first amount used will be either more or less alkaline than the last-used. This often results in having a product 3,223,646 Patented Dec. 14, 1965 which, for some hard-surface cleaning purposes may be too alkaline, thus injuring the surface to be cleaned, wh1le in other instances, has an insufficient alkalinity to clean the surface completely.

A further disadvantage in the presently used mechanically mixed hardsurface cleaning detergent compositions is in the various, often expensive, manipulative steps required to provide such a composition. For example, it is necessary that the particle size of both the phosphate material and the sodium carbonate material, as well as that of any other solid materials in the composition, be closely controlled so as to be substantially equal in order that a good mechanical mix can be obtained. This, of course, requires various screening operations with resulting over and undersize particles which must be disposed of in some manner. Additionally, the formation of such a mechanically mixed composition requires numerous mixing or agitation steps in order to effect, at least initially, a uniform dispersion of the various components of the composition. These manipulative steps have been found to be somewhat expensive, both in terms of the equipment required as well as the time which is necessary to carry them out. Notwithstanding the expensive and time-consuming steps which are required, however, the finished product which is obtained is still subject to a degeneration to a non-homogeneous mixture after normal handling.

It has now been found that these ditficulties, as are presently encountered in the production of a mechanically mixed detergent composition, can be overcome by forming this detergent composition by means of a chemical reaction rather than a mechanical dispersion.

It is, therefore, an object of the present invention to provide a detergent composition, particularly one which is applicable to hard-surface cleaning, which composition is not subject to the disadvantages presently encountered in the mechanically mixed compositions.

Another object of the present invention is to provide a detergent composition having applicability as a hardsurface type cleaner, which composition, when dissolved in water, has substantially the same composition, in terms of Na O and P 0 content, as the presently used composition prepared by mechanical mixing.

A further object of the present invention is to provide a completely homogeneous hard-surface detergent composition without the expensive and timeconsuming screening, grinding, and mixing or agitating steps presently required in forming such compositions.

These and other Objects will become apparent to those skilled in the art from the description of the invention which follows.

In this description and the claims it is to be understood that in referring to alkali metal compounds, it is intended to nclude compounds of lithium, sodium, potassium, cesium, and rubidium. Because of their low cost and ready availability the compounds of sodium are preferred, and for this reason primary reference, hereinafter, will be made thereto. This is not to be taken as a limitation, however, but merely as being illustrative of the present invention.

The composition of the present invention envisions a detergent composition comprising at least .one phosphate of the formula: x y 4 2 where M is an alkali metal, x and y are positive integers greater than 0, the sum of which is 3, and a is a number from 0 to 2, at least one alkali metal compound selected from the group consisting of carbonates, bicarbonates, sesquicarbonates, and mixtures thereof, said composition having a mole ratio of M O:P O greater than about 3:1, and a pH, in a 1% water solution, greater than about 7.5, said composition resulting from a chemical reaction, in

and meta silicates, as Well as the various liquid silicate compositions, such as those having an Na O:SiO ratio Within the range of about 1:33 to 1:1. silicate various organic surfactant materials, either nonionic, anionic, or cationic, may also be used, which matcrials may be either in liquid or solid form. Examples of such materials which may be used are found in the following tables:

In addition to a NON-IONIC SURFACTANTS Trade Name Manufactuter Description Triton NE Triton X-100 Igepal CO630 Antarox A200 Ceriak 1,300.. Ceriak Nl00 Dergon OM-..

Atlas Powder Co Rohm & Haas Co Monsanto Chem. Co Monsanto Chemical Monsanto OhemicaL Alrose Chem. Co- Alrose Chem. Co Alrose Chem. Co Gen. Aniline & Film Co E. F. Houghton & Co..- E. F. Houghton & Co. Arkansas Co Alkylated aryl polyether alcohol.

Alkylated aryl polyether alcohol.

Alkyl aryl polyethylene glycol ether.

Alkyl aryl polyethylene glycol ether.

Polyoxyethylene ester of mixed fatty and resin acids (Tall oil). Polyoxyethylene ester of mixed fatty and resin acids (Tall oil). Polyoxyethylene ether.

Polyoxyethylenethio ether.

Polyoxyethylenethio ether.

Fatty alkylol amine condensate.

Fatty alkylol amine condensate.

Fatty alkylol amine condenstte.

Alkyl aryl polyethylene glycol.

Alkyl polyoxyethylene alcohol.

Polyethanolamine fatty acid condensate.

Amino fatty ester.

Neutronyx 600 Onyx Oil & Chem. Co Aromatic polyglycol ether condensate. N onic 218 Sharples Chemicals, Inc Polyethylene glycol tertdodecyl thioether. 1011 E. F. Drew & Co A secondary amide of lauric acid.

ANIONIC SURFACTANTS Trade Name Manufacturer Description Naccolene F Natl. Aniline Div. Allied Chem. & Dye Corp Modified alkyl aryl sulfonate. Nacconol NR-" Natl. Aniline Div. Allied Chem. & Dye Corp Alkyl aryl sulfonate.

Nacconol LAL. Santomerse D Ultrawet 30E Orvus WA Duponol LS Duponol SN Du'ponol WAT Aerosol 18 Miranol HM Pactivex Natl. Aniline Div. Allied Chem. & Dye Corp Monsanto Chem. Co Atlantic Refining Co Proctor & Gamble Co E. I. du Pont E. I. du Pont American Cyanamid Co- Alrose Chemical Co General Aniline & Film. General Dyestuffs Corp. General yestuffs Corp. Imperial Chem. Ind... M. Michel & Co

Sodium lorol sulfoacetate.

Decyl benzene sodium sulfonate.

Alkyl benzene sodium sulfonate.

Sodium salt of lauryl sulfate.

Technical oleyl sulfate.

Sodium lorol sulfate.

Triethanolamiue salt of alcohol sulfates.

N-octa decyldisodium sulfo succinamatc.

Fatty amide sulfate.

Sodium palmitoyl methyltaurate;

Sodium oleyl p-anisidine sulfonate.

Lauroyl imidazolene. Sodium dodecyl toluene sulfonate.

Triton W-30 Rohm & Haas Co Sodium salt of alkylated aryl polyether sulfate.

CATIONIC SURFACTANTS- Trade Name Manufacturer Description Hyamine 1622 Rohm & Haas Co Di-lilslobuityl phenoxy ethoxy ethyl dimethyl benzyl ammonium c on e. Onyxide Onyx Oil & Chem Alkenyl dimethyl ethyl ammonium bromide. Roccal Winthrop-Stcarns, Inc Alkyl dimethyl benzyl ammonium chloride.

NCH2 Alro Amines-C, O-S Alrose Chem. Co CHs(CHz) C ll TCH2 R Amine 220 Carbide & Carbon Chem. Corp RfiJNCH2CH2OH NCH2CHz Germ-i-tol Octab Oronite Quaternary-ATM50 LPC Armour & Co

Rhodes Chem. Co-

Emulsol Corp Fine Organics, Inc. Rhodes Chem. Co

Oronite Chem. Co-

Hooker Elec.-Chem RN(CHa)sCl; R=1218 carbon atoms.

Cetyl trimethyl ammonium bromide-CmHaaN(CHa)aBr.

CH3(CH2) ..C O O CHzCHzNHC O CH2I I-Cl OZHE Dimethyl benzyl lauryl ammonium chloride. Octadecyl dimethyl benzyl ammonium chloride- CisHs7(CHs)z1 |T-(CsH CH C1 N-alkyl benzyl N-N-N trimethyl ammonium chloride.- Lauryl pyridinium chloride-C 0H5NC zHzu In general, the composition of the present invention is prepared by reacting an alkali metal carbonate-containing material with phosphoric acid, the amounts of these reactants being sufiicient to provide a product having a mole ratio of alkali metal oxide to phosphous pentaoxide, e.g. Na OzP O which is greater than about 3:1. This is preferably done by adding the phosphoric acid to the dry alkali metal carbonate-containing material, typically sodium carbonate, with agitation, in the amount of at least about 1.5 moles of sodium carbonate to 1 mole of H PO The addition of the phosphoric acid to the sodium carbonate is made over a sufficiently long period of time so as to provide complete mixing and reaction of these materials and to prevent the formation of lumps in the reaction mixture. The actual addition time will, of course, depend upon the type of mixing apparatus which is used so that, with more efiicient mixing, a shorter addition time can be used. It is to be appreciated that, although lumping in the reaction mixture is not desired, if lumps do occur, the product can still be used by subjecting it to a grinding or crushing operation so as to reduce the lumps to a usable size.

It has not been found that the reaction temperature is extremely critical or that it must be maintained within narrow limits in order to produce the product of the present invention. Thus, it has not been found to be necessary either to heat the reaction mixture or to cool it in order to maintain some desired reaction temperature. It has been found to be preferable, however, that the reaction temperature not exceed about 100 C. for any prolonged period of time during the reaction. When temperatures of this magnitude are maintained over a long period, it has been found that there is an excessive reaction loss, in terms of water and carbon dioxide given off, which loss is desirably avoided, if possible.

The composition produced by this reaction contains at least one phosphate, having the formula:

where M is an alkali metal, x and y are positive integers greater than 0, the sum of which is 3 and a is a number from to 2, and at least one alkali metal compound selected from the group consisting of carbonates, bicarbonates, sesquicarbonates, and mixtures thereof. The phosphate which has been found to predominate in this composition is the di-alkali metal acid phosphate, e.g., Na HPO although the mono-alkali metal acid phosphate, e.g., NaH PO is also formed. These phosphates have been found to be either anhydrous, monoor di-hydrated, with the di-hydrate appearing to predominate over the mono-hydrate. Thus, the predominant phosphate in the present composition is Na HPO or its dihydrate,

with lesser quantities of the mono sodium phosphate, NaI-I PO or its di-hydrate, NaH PO -2H O being formed. It is to be appreciated, of course, that whether the anhydrous or hydrated form of the phosphate is produced will depend upon the amount of Water available in the reaction mixture.

The alkali metal component of the composition of the present invention has been found to be sodium carbonate, sodium sesquicarbonate, sodium bicarbonate, or mixtures of these materials. Inasmuch as the reaction mixture contains an excess of the sodium carbonate in order to provide the necessary Na O:P O ratio of greater than about 3: 1, there would, obviously, be some sodium carbonate in the product, the amount depending upon the initial starting ratio of sodium carbonate to phosphoric acid. Although it is not certain, it is believed that, in the reaction which takes place, carbon dioxide is given off which then reacts with the excess sodium carbonate to form sodium bicarbonate. Where water is also present in the reaction mixture, there will be a further reaction of the sodium bicarbonate with any excess sodium carbonate to form sodium sesquicarbonate or trona. Thus, depending upon the amount of sodium carbonate which is initially used in the reaction mixture, as well as the amount of Water present, the final product of the present invention will contain at least one of the alkali metal compounds selected from the carbonates, bicarbonates, and sesquicarbonates and, generally, will contain more than one of these materials, the most likely combination being the carbonate and the sesquicarbonate. It is to be noted, once again, that the product of the present invention is the result of a chemical reaction so that the alkali metal compound will be intimately combined with the phosphates and will not be merely a mechanical mixture.

In the preparation of the composition of the present invention, any type of phosphoric acid may be used. Although the orthophosphoric acid (H PO is the most common and least expensive of the phosphoric acids, solutions of the various other phosphoric acids, such as pyrophosphoric acid (H P O tripolyphosphoric acid and metaphosphoric acid (HPO may also be used. In addition to these, more concentrated phosphoric acids, which are mixtures of the various forms of phosphoric acid, may also be used. Exemplary of such materials is a concentrated phosphoric acid, sold under the name Phospholeum. This aci dhas a P 0 content equivalent to 105% H PO and has the following typical analysis:

Percent Orthophosphoric acid (H PO 58 Pyrophosphoric acid (H P O 38 Tripolyphosphoric acid (H P O 3.5 Higher polyphosphoric acids, as (HPO e.g.

(H6P4013), etc

all of the above being percent by Weight of the total composition.

In actual practice the use of this more concentrated phosphoric acid has been found to give definite advantages over the other phosphoric acids, such as orthophos phoric acid. Although the more concentrated phosphoric acid is slightly more expensive than orthophosphoric acid, because of its greater P 0 content, its cost, based on the P 0 content, is about the same as orthophosphoric acid. Additionally, it has been found that, when this more concentrated phosphoric acid is reacted with the soda ash in the method of the present invention, there is substantially no reversion of the pyrophosphoric acid content of the acid to the ortho form. Thus, the product produced contains tetrasodium pyrophosphate (Na P O which material is very desirable in a detergent composition because of its sequestering, dispersing and deflocculating action. Accordingly, by the use of a more concentrated phosphoric acid, which is a mixture of various forms of phosphoric acid, a detergent product is obtained, which contains as a part of the chemical reaction product, a sequestering agent, thus making it unnecessary to add such a material to the composition and combine it by means of mechanical mixing.

The concentration of the phosphoric acid used, whether it is a more concentrated mixture of various forms of phosphoric acid or not, has not been found to be extremely critical. Thus, when using orthophosphoric acid, for example, the commercial grade of 85% phosphoric acid may be used. Similarly, various more dilute acids may also be used, such as 45%, and 25%. Inasmuch as it is desirable that the product, prepared by the present method, is dry and free-flowing, the phosphoric acid concentration should not be so low that excessive quantities must be added to the reaction mixture when the desired P 0 content is obtained. As has been set forth hereinabove the amount of water present in the reaction mix is the principal determining factor as to Whether the anhydrous or hydrated forms of the alkali metal phosphates are produced, and also whether the sodium bicarbonate produced will combine with the sodium carbonate to produce sodium sesquicarbonate. Inasmuch as any water, present in the reaction mix in excess of that required to perform the above two functions, will tend to make the final product somewhat tacky, thus necessitating an additional drying step, it is preferred that the phosphoric acid used not have a concentration less than about 20% by weight. Again, it will be appreciated, that the choice as to the concentration of the phosphoric acid which is used will be dictated according to the composition which is desired in the final product. Where a detergent composition is required, which contains a hydrated sodium phosphate, or which contains large amounts of trona, the more dilute phosphoric acid will be used. Similarly, where the anhydrous forms of the sodium phosphate are required, or smaller amounts of trona, the converse is true. It is believed that those skilled in the art will be able to determine in each instance the type of composition which is required and, hence, the concentration of phosphoric acid which should be used.

The alkali metal carbonate-containing material, which is reacted with the phosphoric acid to obtain the composi tion of the present invention, may be the alkali metal carbonate itself, such as sodium carbonate, or it may be a compound containing the alkali metal carbonate, such as sodium sesquicarbonate. Generally, for reasons of cost consideration, it is preferred to use the less expensive alkali metal carbonates, such as sodium carbonate, rather than the more expensive sesquicarbonate. Any of the available forms of the alkali metal carbonate, e.g., sodium carbonate, may be used, including the socalled light ash and dense ash. These materials are, of course, sodium carbonates which differ only in particle structure and bulk density. Additionally, a new and unique form of sodium carbonate, having a granular particle configuration but a low bulk density, may also be used. This material has a bulk density comparable to that of light ash, but, unlike light ash, which is extremely fine, its particle configuration is granular, very similar in size to that of dense ash. In view of the unique characteristics of this material, which characteristics will be referred to in more detail hereinafter, it is the preferred form of sodium carbonate for use in the method of the present invention. For the sake of convenience, this material will henceforth be referred to as granular light ash.

This preferred granular light ash, and its method of preparation, are described in a copending application, Serial No. 119,321, filed June 26, 1961, now Patent No. 3,188,170.

As is set forth in this copending application the granular light soda ash is prepared by mixing a hydrated sodium carbonate with sodium bicarbonate in a proportion of bicarbonate to hydrated carbonate, in terms of alkali metal carbonate equivalents, substantially within the range of :1 to 1:2, so as to form substantial amounts of sodium sesquicarbonate in the mixture. Thereafter, the mixture is rapidly heated to a temperature above that at which decomposition of the bicarbonate and sesquicarbonate began, and the carbonate becomes anhydrous. This temperature is maintained for a sufiicient period of time to effect decomposition of the mixture while carbon dioxide and water, evolved from the mixture during the heating, are removed. The sodium carbonate product thus produced is then recovered. This product is characterized by larger particles than those obtained by the calcination of an alkali metal bicarbonate alone and a bulk density within the range of about 25 to 45 lbs. per cubic foot. This sodium carbonate product is further characterized by having spheroidal particles of the size such that about 65 to 100% is retained on a 100 mesh screen, and upwards of 92% is retained on a 200 mesh screen.

The use of this granular light ash has been found to be particularly advantageous in forming the present composition in that, by its use, a dry granular composition can be formed even when using relatively poor mixing to combine the carbonate material and the phosphoric acid. Additionally, this granular light ash has exceptional absorption characteristics Which are particularly advantageous when liquid silicates and organic surfactants are to be included in the subject composition. In this regard it has been found that liquid silicates and non-ionic, cationic, and anionic surfactants can be absorbed by this granular light ash in amounts up to as high as 30% or 35% by weight of the total composition, i.e., the granular light ash plus the silicate or surfactant. Accordingly, where these materials are desired in the present detergent composition, the surfactants can be admixed With the phosphoric acid prior to the time it is added to the granular light ash, and the resulting mixture then combined with the ash. In the case of the silicates they can be added subsequently to the phosphoric acid. In this way, the liquid silicates and/or organic surfactants are absorbed by the granular light ash and the phosphoric acid reacts therewith toform the product of the present invention in dry, granular form, having the silicate and surfactants intimately dispersed therein. Thus, the necessity for any mechanical mixing step is completely eliminated. This granular light ash is further advantageous in view of its rapid solubility in water as compared to conventional light ash and dense ash. For example, comparing the solubility rate of g. of material in 200 ml. of Water, the granular light ash dissolves in 22 seconds, while 26 seconds are required for conventional light ash, and 47 seconds for conventional dense ash. It is for these reasons that the granular light ash, as described in U.S. Serial No. 119,- 321, is the preferred alkali metal carbonate material for forming the detergent composition of the present invention.

As has been set forth hereinabove, the alkali metal carbonate-containing material, preferably the granular light ash, and a phosphoric acid, are combined in amounts which will give a reaction mixture, and hence, a product, having a mole ratio of Na OzP O which is greater than about 3:1. In order to attain this mole ratio of Na O:P O it is necessary that the initial reactants are combined in an amount so that the mole ratio of sodium carbonate (Na CO to phosphoric acid (H PO is greater than about 1.5 :1. A preferred ratio of sodium carbonate to phosphoric acid (H PO is Within the range of about 3:1 to 6:1. Although ratios of sodium carbonate to phosphoric acid, which are greater than 6:1, may be used, the product produced from such ratios has such a high alkalinity that it is not usable for many applications. Accordingly, the preferred upper ratio of sodium carbonate to phosphoric acid (H PO is about 6:1, although this is not to be taken as limitmg.

It is believed that those skilled in the art will appreciate that, where the lower ratios of sodium carbonate to phosphoric acid are used, there will, obviously, be less excess sodium carbonate in the reaction mixture. Accordingly, this means that less water can be tolerated in the reaction mixture and still obtain a product which is not tacky. In these circumstances, it will be necessary to use the more concentrated phosphoric acids since, as has been set forth hereinabove, additional quanities of water are introduced into the reaction mixture when using the more dilute phosphoric acid. Thus, when using a sodium carbonate to phosphoric acid (H PO mole ratio of about 2:1, it is not feasible to use a phosphoric acid having a concentration of less than about and still obtain a dry, granular product. In contrast, when the mole ratio of sodium carbonate to phosphoric acid (H PO used is 6:1, phosphoric acid concentration as low as about 25%, or less, can be used without adversely affecting the free-flowing character- 9 istics of the product produced. Again, it will be appreciated by those skilled in the art that the mole ratio of sodium carbonate to phosphoric acid, which is used, will depend upon the constituents which are desired in When the sodium carbonate material was placed in the blender and the covers sealed, rotation of the blender and the mixing bar was begun. The respective rotational speeds of the blender and mixing bar were 35 rpm. and 1700 rpm. The phosphoric acid of the desired concenthe detergent product. Where, for example, a product 5 is desired having only a small amount of sodium cartration was fed into the sodium carbonate material bonate or sodium sesquicarbonate, the lower mole ratios through 0.01" openings in the mixing bar. After the of sodium carbonate to phosphoric acid, such as 2:1 or phosphoric acid addition was completed, the temperature 321, will be used. Alternatively, where large amounts of the hot product was measured. Mixing of the product of sodium carbonate and/ or sesquicarbonate are desired Was then continued for about minutes so as to provide in the product, the higher ratios of sodium carbonate for partial cooling and absorption of water vapor. The to phosphoric acid, such as 5:1 or 6:1, Will be used. weight of the product was then recorded and the percent It is believed that those skilled in the art will readily be Welght reaction loss determined. able to determine the mole ratio of sodium carbonate The amounts of the reactants which were used were to phosphoric acid which is desired, in combination 1 detefmlnfid y the 111016 ratio of 2 3 s 4- with the concentration of phosphoric acid which is to ach mo e of Na CO 106 g. were used. For each mole be used, depending on the substituents which are desired f H PO 98 g. Were used. Where the phosphoric acid in the fi i h d product, used had a concentration of 85%, 115.3 g. were used for In order that those skilled in the art may better undereach mole of H PO required. Similarly, when using acid stand the present invention and the manner in which it 2 concentrations of 65, 45 and percent, the following may be practiced, the following specific examples are quant1t1es were used for each mole of H PO required: given. G

In the following examples the phosphoric acid used is 65% 8 orthophosphoric acid of varying concentrations. The

0 217.8 procedure followed conslsted 1n coohng the orthophos- 25 25% 392 0 phoric acid to 0 C. in a beaker with Dry Ice. The temperature of the sodium carbonate-containing material Using this procedure, the following runs were made:

PRODUCT COMPOSITION-PERCENT BY WEIGHT 6 5 G I ,3 N320 P205 C01 1110 g "'3 E 215 a 5 "5 a H 5-. ,q' o o 0 4 0 r-4 0: E A9 "4'45 P :-4 L o .i Example 35 :5 as 23 3 a; g m0 5 3 ,0 E10 3 T3 4 Page *5 .-r 445%,, 5 .4 .735 53 H Q14 o 4 t. O S .4 3 +5 4. *5 49 rd m 8 c1! :3 U, 1.. a :6 1. 1:9 O 4.. i '2! 06 56 0 o 0 g 5160 a :1 Duo 8 :4 213-708 N m 0.5 O M- 02 r.OK NE 853 wi l a o 0541-. I; *5 33g n 33g S gr, +5 3;, m 2 :5 m e: 91 3 1 4 E 1 6 1 1 6: 6' 2 :1 in

used Was room temperature, i.e., 24 C. In Examples 1 through 12 the sodium carbonate-containing material was the granular light ash prepared in accordance with the procedure set forth in US. Serial No. 119,321. In Examples 13 through 16 the sodium carbonate material used was commercial light ash, having a bulk density of 34.2 lbs. per cu. ft., while Examples 17 and 18 used commercial dense ash, having a bulk density of 61 .2 lbs. per cu. ft. The bulk density of the granular light ash used in Examples 1 through 12 was 33.7 lbs. per cu. ft. The sodium carbonate material was placed in a Patterson- Kelley twin shell blender (8 qt. liquids-solids model) just prior to reaction time. This blender is manufactured by the Patterson-Kelley Co., Inc., of East Stroudsburg, Pa. It consists of a V-shape container, provided with covered openings in the end of each leg of the V, through which the material to be blended is charged, and a discharge opening in the apex of the V. The blender is supported by a shaft which passes through both legs of the V about three-fourths of the way up the legs from the apex. The entire blender rotates around this shaft. Additionally, a mixing bar is provided on this shaft, which rotates independently of the blender and through which liquid components are added to the dry materials in the blender.

All of the products obtained in the above examples were dry and free-flowing. Those products obtained in Examples 1 through 12, which used the granular light ash as a starting material, were also granular in form. Simi larly, the products obtained in Examples 13, 17 and 18 were also granular in form. The products obtained in Examples 14 through 16 were in the form of a powder. X-ray analysis of all of these products shows that they contain Na HPO Na CO and sodium sesquicarbonate, in varying concentrations depending upon the initial mole ratio of Na CO :H PO Additionally, depending upon the concentration of phosphoric acid used, both the anhydrous and the dihydrated forms of the were present. It is to be noted that, in the analysis of the product composition, the weight percentages of the Na O, P 0 and CO were obtained by experimental analysis. With regard to the water in the composition the column, headed Theoretical-as free H O refers to the amount of water which should be present, based upon the water added in the initial reaction mixture. The column, headed Total B 0, is a calculated value arrived at by subtracting the sum of the anhydrous compo- 1 1 nents of the mixture, calculated as Na HPO Na CO and NaHCO from 100%. This total amount of water represents the water which is held in the composition as water of hydration for the components, as well as any free water which may be absorbed in the product.

Example 19 By way of comparison an additional run is made, using the procedure as set forth hereinabove with the granular light ash as the sodium carbonate material, and using 85% orthophosphoric acid. The mole ratio of is 1:1 The phosphoric acid is added over a period of 12 minutes, and the final temperature of the product is 95 C. There is a reaction loss in this experiment of 19.2%. The mole ratio of N21 O:P O in the product is 2:1, and the product has the following composition in Experimental analysis of the Na P O content of this product indicates that the actual content of this component is 19.60% before being adjusted for the reaction loss, and is equal to 17.70% after being adjusted for the reaction loss. This value corresponds quite closely to the theoretical amount of 17.36%. The pH of a 1% solution of the product of this example is 9.71, and the bulk density of the product is 41.3 lbs. per cu. ft. as compared to a bulk density of 33.7 lbs. per cu. ft. for the granular light ash. The product obtained is dry, in granular form, and is free-flowing.

From this example it is seen that, when a concentrated phosphoric acid, made up of a mixture of various forms of phosphoric acid, including pyrophosphoric acid, is used in the method of the present invention, there is no reversion of the pyrophosphate in the composition to the orthophosphate form.

Example 21 percent by weight: 111 g.. of a non-ionic surfactant, Triton X-100 (alkyl- Na o P 0 00 H O Actual Actual Actual Theo Actual Adj. for Theo- Actual Adj. for Theo- Actual Ad for Theoretical Total retical Reaction retical Reaction retical Reaction as free 11 0 Loss Loss Loss The pH of a 1% solution of this product is 7.44, and the product has a bulk density of 48.1 lbs. per cubic foot. Although the product of this reaction is granular in form, it is quite damp and not free-flowing.

By a comparison of this example with the above Examples 1 through 18 it is seen that, when the product has a mole ratio of Na OzP O which is less than about 3:1, the pH of a water solution of this product is sufficiently non-alkaline as to greatly limit the use of the material. Additionally, it is seen that, unlike the products of Examples 1 through 18, the material produced hereinabove is not free-flowing.

Example 20 An additional experiment is made, using the apparatus and procedure as set forth for the preceding examples. In this experiment the sodium carbonate material is the granular light ash and the phosphoric acid is a concentrated phosphoric acid having the following composition in percent by weight:

Percent H PO 58 H P O 38 H P O 3.5 Polyphosphoric acids as HPO 0.5

These materials are reacted in a mole ratio of Na CO :H PO

Percent Na HPO 25.70 Na P O 17.36 NP3010 NaPO 0.20 Na2CO3 H CO 20.02

ated aryl polyether alcoholU.S. Patent 2,504,064) is mixed with 712 ml. of water. To this is added 518 ml. of a H PO and the resulting mixture cooled to about 10 C. Using the procedure and apparatus as set forth for Examples 1 through 18, the phosphoric acid solution is added to 4,000 g. of the granular light ash. The resulting composition was found to be dry and free-flowing, having an Na O content of 42% by weight, a P 0 content of 8% by weight, and a non-ionic surfactant content of 2% by weight.

Comparative cleaning tests with this product and commercially available solid and liquid hard surface cleaners showed a decided advantage, in terms of cleaning power for the present composition over the other commercially available compositions tested.

Example 22 The procedure of the preceding example is repeated with the exception that the initial reactant composition consists of 4,000 g. of the granular light ash, 1,540 g. of 40% H PO 70 g. of the Triton X-100, and g. of dodecyl benzene sulfonic acid. These materials are reacted, using the procedure and apparatus of the preceding example. The resulting product is found to have an Na O:P O mole ratio of about 12:1 and is a dry, granular free-flowing composition. Comparative washing tests, using this product and commercially available solid and liquid hard surface cleaners showed that the composition of this example is superior in cleaning power to the other cleaners tested.

From the foregoing, it has been shown that, by the method of the present invention, a detergent composition can be prepared, which composition is at least equal in cleaning power to other commercially available hard surface cleaners. The composition of the present invention has been found to be a granular, free-flowing product, having the various constituents thereof intimately and homogeneously dispersed throughout the composition. The homogeneous characteristics of the present composition are the result of the fact that this composition is obtained by means of a chemical reaction, rather than by mere mechanical mixing.

It is to be understood that, although the invention has been described with specific reference to particular embodiments thereof, it is not to be so limited, since changes 13 and alterations therein may be made which are within the full intended scope of this invention as defined by the appended claims.

What is claimed is:

1. A dry, free-flowing detergent composition, consisting essentially of a mixture of at least one phosphate of the formula:

M H PO4 aHgO where M is an alkali metal, x and y are positive integers greater than 0, the sum of which is 3, and a is a number from to 2, and at least one alkali metal compound selected from the group consisting of carbonates, bicarbonates, sesquicarbonates, and mixtures thereof, said composition having a mole ratio of M O:P O from about 3:1 to about 12:1 and a pH in a 1% water solution, greater than about 7.5, said composition resulting from a chemical reaction between dry solid particles of an alkali metal compound selected from said group and a phosphoric acid, in proportions such as to give said mole ratio, and obtained by intimately dispersing an aqueous phosphoric acid solution in a body of dry solid particles of an alkali metal carbonate with mechanical agitation, while maintaining the temperature of the mixture not substantially in excess of 100 C.

2. A dry, free-flowing, detergent composition, consisting essentially of a mixture of at least one phosphate of the formula:

Na H PO aH O where x and y are positive integers greater than 0, the sum of which is 3, and a is a number from 0 to 2, with at least one sodium compound selected from the group consisting of carbonates, bicarbonates, sesquicarbonates, and an organic surface-active agent selected from the group consisting of anionic, non-ionic and cationic compounds, said composition having a mole ratio of Na O:P O within the range of about 4:1 to 12:1, and a pH in a 1% water solution greater than about 9.5, said composition resulting from intimately dispersing an aqueous solution of a phosphoric acid and an organic surface-active agent of said group in a body of dry solid particles of said sodium compound so as to effect a chemical reaction between said sodium compound selected from said group and said phosphoric acid, agitating the resulting mixture while maintaining the temperature thereof below about 100 C.

3. A method of preparing a dry, free-flowing detergent composition, which comprises intimately dispersing an aqueous solution of a phosphoric acid in a body of dry solid particles of an alkali metal carbonate selected from the group consisting of carbonates, bicarbonates, sesquicarbonates and mixtures thereof, in proportions such as to give an alkali metal oxide: phosphorus pentaoxide ratio from about 3 :1 to 12: 1, so as to effect a chemical reaction therebetween, agitating the resulting mixture while maintaining said mixture at a temperature not substantially in excess of about 100 C. until the said reaction is complete, and recovering the resulting product characterized by a pH in a 1% Water solution, greater than about 7.5.

4. A method of preparing a dry, free-flowing detergent composition, which comprises intimately dispersing an aqueous solution of a phosphoric acid in a body of dry solid particles of a sodium carbonate material in an amount such that the Na CO :H PO mole ratio is from 1.521 to 6:1, so as to effect a chemical reaction therebetween, agitating the resulting mixture while remaining said mixture at a temperature not substantially in excess of about C. until the said reaction is complete, and recovering the resulting product characterized by an Nazo 1 P205 mole ratio greater than about 3:1 and a pH, in a 1% water solution, greater than about 7.5.

5. The method as claimed in claim 4, wherein the phosphoric acid is a concentrated phosphoric acid containing a mixture of phosphoric acids, including pyrophosphoric acid.

6. A method of preparing a dry, free-flowing detergent composition, which comprises intimately dispersing an aqueous solution of an orthophosphoric acid in a body of dry solid particles of anhydrous sodium carbonate in an amount such that the mole ratio of Na CO :H PO is from about 1.5:1 to about 6:1 so as to eifect a chemical reaction therebetween, agitating the resulting mixture while maintaining said mixture at a temperature not substantially in excess of about 100 C. until the said reaction is complete, and recovering the resulting product characterized by an Na O:P O mole ratio greater than about 3:1 and a pH in a 1% water solution, greater than about 7.5.

7. A method of preparing a dry, free-flowing detergent composition which comprises adding an organic surfaceactive agent selected from the group consisting of anionic, non-ionic, and cationic compounds, to an aqueous solution of orthophosphoric acid, the resulting solution having an H PO content of at least about 20% by weight, intimately dispersing the resulting mixture in a body of dry solid particles of sodium carbonate in an amount such that the resulting mixture has an Na CO :H PO mole ratio from about 1.5 :1 to about 6:1, so as to effect a chemical reaction therebetween, agitating the resulting mixture while maintaining said mixture at a temperature not substantially in excess of about 100 C. until the said reaction is complete, and recovering the resulting product which contains at least one phosphate of the formula:

Na H PO aH O where x and y are positive integers greater than 0, the sum of which is 3, and a is a number from 0 to 2, at least one sodium compound selected from the group consisting of carbonates, bicarbonates, sesquicarbonates, and mixtures thereof, and the organic surface-active agent, said composition being characterized by an Na2OZP2O5 mole ratio greater than about 3:1 and a pH, in a 1% water solution, greater than about 7.5.

References Cited by the Examiner UNITED STATES PATENTS 1,642,244 9/1927 Howard 23-407 1,648,656 11/1927 Meyers 23107 1,921,505 8/1933 Chesny 2363 1,961,127 6/1934 Coleman 23107 2,017,828 10/1935 Booth 252- 2,351,559 6/1944 Trefiier 252-135 2,502,881 4/1950 Parker 252109 2,515,880 7/1950 MacMahon et al. 252135 2,811,419 10/1957 Hartlapp et al. 252-135 XR 3,086,844 4/1963 Beltz et al 23107 JULIUS GREENWALD, Primary Examiner. 

1. A DRY, FREE-FLOWING DETERGENT COMPOSITION, CONSISTING ESSENTIALLY OF A MIXTURE OF AT LEAST ONE PHOSPHATE OF THE FORMULA: MXHYPO4$AH2O 